PROJECT REPORT ON HEAVY METALS IN VEGETABLES AND FRUITS; AND RISK ASSESSMENT : LITERATURE REVIEW

SUBMITTED TO DR. SIBY JOHN PROFESSOR ENVIRONMENTAL ENGG

SUBMITTED BY ABHISHEK KOUL 13201001 M.E ENVIRONMENTAL ENGG

List of Contents
Topic Page No. 1. Introduction ........................................................................1 2. Materials and Methods........................................................2 2.1 Selection of Sampling area and sampling........................2 2.2 Sample Preparation.........................................................2 2.3 Digestion of Samples.......................................................2 3. Analysis of Hea y Metals......................................................3 3.1 Atomic Absorption Spectrometry....................................3 3.2 Data Analysis....................................................................5 !. Per"issi#le Li"its for hea y "etals and effects.....................$ 4.1 Limits for heavy metals in food st ffs..............................5 4.2 !ealth effects of heavy metals........................................." 5. Case %tudies..........................................................................& 'eferences............................................................................12

1. Introduction
Vegetables and fruits consumption account for the natural uptake of vitamins, minerals, fibres, etc in humans. These are sources of essential nutrients and antioxidants and as such act as neutralizing agents for acidic substances formed during digestion. Environmental pollution is now-a-da s a cause of concern. !eav metal pollution of agricultural soil and vegetables is one of the most severe ecological problems on a world scale. The food chain contamination is the ma"or pathwa of heav metal exposure for humans. #ome trace metals are essential in plant nutrition, but plants grown in the nearb zone of industrial areas displa increased concentration of heav metals. Vegetables and fruits act as $small accumulators% of different heav metals as a function of soil&air&water pollution degree. 'apid and unorganized industrialization and urbanisation have contributed to the elevated levels of heav metals in the urban environment in the developing countries. !eav metals are non-biodegradable and persistent environmental contaminants which ma be deposited on the surfaces and then absorbed into the tissues of the vegetables. Emissions of heav metals from the industries and vehicles ma be deposited on the vegetable surfaces during their production, transport and marketing. (lants take up heav metals b absorbing them from deposits on the parts of the plants exposed to the air from polluted environment as well as from contaminated soils. )ater contamination b heav metals in some areas is practicall inevitable due to natural process *weathering of rocks+ and anthropogenic activities *industrial, agricultural and domestic effluents+. These elements, at concentrations exceeding the ph siological demands of vegetables, not onl could administer toxic effect in them but also could enter food chains, get biomagnified and pose a potential threat to human health. !eav metal contamination in agricultural soils from waste water irrigation is of serious concern due to its implications on human health. Enormous volumes of wastewater are being released, which is increasingl being utilized as a valuable resource for irrigation in urban and peri-urban agriculture. ,t drives significant economic activit , supports countless livelihoods particularl those of poor farmers, and substantiall changes the water -ualit of natural water bodies. )aste water from industries of mining, electroplating, paint or chemical laboratories often contains concentrations of heav metals, including .n, /u, (b, 0n, 1i, /r, /d. /ontinuous irrigation of agricultural land with sewage and industrial waste water ma cause heav metal accumulation in soil and vegetables. (rolonged consumption of unsafe concentrations of heav metals through foodstuffs ma lead to chronic accumulation of heav metals in various organs of humans such as kidne s and liver, causing disruption of numerous biochemical processes, leading to cardiovascular, nervous, kidne and bone diseases. #ome heav metals such as /u, .n, 0n, /o and 0o act as micronutrients for the growth of animals and human beings when present in trace -uantities, whereas others such as /d, 2s and /r act as carcinogens, and !g and (b are

associated with development of abnormalities in children. 2lso long term intake of /d is reported to cause renal, prostate and ovarian cancers.

2. Materials and Methods

2.1 Selection of sampling area and sampling 2 particular area is selected for which sampling is to be done. The area might be in the vicinit of the industrial effluent dumping site or an other area prone to the heav metals in the form of pollution from various sources. The samples of vegetables are collected from the agricultural area or can be randoml purchased from the market in the vicinit . 4ifferent t pes of vegetable samples are to be collected in which the heav metals concentration is to be determined. #oil samples are also to be collected b digging out from the )astewater ,rrigated *)),+ sites. ,t should be air dried, crushed and stored at ambient temperature before anal sis. 2lso the water used for the irrigation purpose is collected, conc. !156 added to avoid microbial activit . The samples are then kept in refrigerator before digestion. #amples of soil and water from /lean )ater ,rrigated */),+ sites are also taken in order to determine the Enrichment 7actor. 2.2 Sample Preparation The vegetables are first washed with distilled water to remove the dust and dirt particles over the surface. Edible portions are first separated and then cut into small pieces. ,t is then weighed to determine fresh weight and the oven dried at a temperature of about 89 :/ for a certain period of time. The dr samples are then crushed using a mortar or a stainless steel blender and passed through a 3mm mesh size sieve. The resulting fine powder is kept a room temperature before anal sis. The soil samples are also air dried, crushed and passed through 3mm mesh size sieve and stored at room temperature before anal sis. 2.3 Digestion of samples 2.3.1 Soil and plant samples #oil and plant samples *1 g+ are to be digested b adding 1; ml of tri-acid mixture of !3#5<, !156 and !/l until a transparent solution is obtained. 2fter cooling, the digested sample is to be filtered and diluted upto ;9 ml using distilled water. 2.3.2 Irrigation Water ;9 ml of irrigation water sample is digested using 19 ml of concentrated !156 at 89 :/ until the solution becomes transparent. The solution is to be then filtered using filter paper and the solution is diluted upto ;9 ml using distilled water.

3. Analysis of heavy metals /oncentrations of heav metals in the filtrate of the digested samples can be estimated using the 2tomic 2bsorption #pectrophotometer.

3.1 Atomic Absorption Spectrometry 2tomic absorption spectrometr *22#+ is an anal tical techni-ue for -uantitative determination of the chemical elements. ,n anal tical chemistr , the techni-ue is used for determining the concentration of a particular element in a sample to be anal zed. 2tomic absorption is so sensitive that it can measure down to parts per billion of a gram in a sample. The techni-ue makes use of the wavelengths of light specificall absorbed b the element. The correspond to the energies needed to promote electrons from one energ level to another, higher, energ level. 6.1.1 Working Procedure 2toms of different elements absorb characteristic wavelengths of light. 2nal sing a sample to see if it contains a particular element means using light from that element. 7or example with lead, a lamp containing lead emits light from excited lead atoms that produce the right mix of wavelengths to be absorbed b an lead atoms from the sample. ,n 22#, the sample is atomised = i.e converted into ground state free atoms in the vapour state = and a beam of electromagnetic radiation emitted from excited lead atoms is passed through the vaporised sample. #ome of the radiation is absorbed b the lead atoms in the sample. The greater the number of atoms there is in the vapour, the more radiation is absorbed. The amount of light absorbed is proportional to the number of lead atoms. 2 calibration curve is constructed b running several samples of known lead concentration under the same conditions as the unknown. The amount the standard absorbs is compared with the calibration curve and this enables the calculation of the lead concentration in the unknown sample. 3.1.2 T e !ig t Source The common source of light is a $hollow cathode lamp%. This contains a tungsten anode and a c lindrical hollow cathode made of the element to be determined. These are sealed in a glass tube filled with an inert gas, e.g neon or argon, at a pressure of between 1 1m=3 and ; 1m=3. The ionisation of some gas atoms occurs b appl ing a potential difference of about 699=<99 V between the anode and the cathode. These gaseous ions bombard the cathode and e"ect metal atoms from the cathode in a process called sputtering. #ome sputtered atoms are in excited states and emit radiation characteristic of the metal as the fall back to the ground state. 2 t pical atomic absorption instrument holds several lamps each for a different element. The lamps are housed in a rotating turret so that the correct lamp can be -uickl selected.

3.1.3 T e "ptical System and Detector 2 monochromator is used to select the specific wavelength of light = i.e spectral line = which is absorbed b the sample, and to exclude other wavelengths. The selection of the specific light allows the determination of the selected element in the presence of others. The light selected b the monochromator is directed onto a detector that is t picall a photomultiplier tube. This produces an electrical signal proportional to the light intensit . *#ig. 3.1+.

7ig 6.1 3.1.$ Atomisation of Sample Two s stems are commonl used to produce atoms from the sample. 2spiration involves sucking a solution of the sample into a flame> and electrothermal atomisation is where a drop of sample is placed into a graphite tube that is then heated electricall . #ome instruments have both atomisation s stems but share one set of lamps. 5nce the appropriate lamp has been selected, it is pointed towards one or other atomisation s stem. 3.1.% &alibration 2 calibration curve is used to determine the unknown concentration of an element, e.g lead in a solution. The instrument is calibrated using several solutions of known concentrations. 2 calibration curve is produced which is continuall rescaled as more concentrated solutions are used = the more concentrated solutions absorb more radiation up to a certain absorbance. The calibration curve shows the concentration against the amount of radiation absorbed. The sample solution is fed into the instrument and the unknown concentration of the element, e.g lead, is then displa ed on the calibration curve '#ig. 3.2(.

7ig 6.3
<

3.2 Data Analysis 3.2.1 )nric ment #actor To examine the translocation of heav metals from the soil to the edible portion of test plants, and to show the difference in metal concentrations in the plants between the sites, the enrichment factor *E7+ can be calculated b using the formula, E7 ? */oncentration of metal in edible part at )), site&concentration of metal in soil at )), site+ & */oncentration of metal in edible part at /), site&concentration of metal in soil at /), site+ !igher values of enrichment factor *E7+ suggest poor retention of metals in soil and more translocation in plants. 3.2.2 *ealt +isk assessment and daily intake of ea,y metals 2n assessment of the health risk posed in human beings b the consumption of contaminated vegetables can be made b comparing the concentration of the contaminants with national and international safe limits. The dail intake of heav metals through the consumption of the vegetables tested can be calculated according to the given e-uation 4ail intake of heav metals *@g&da + ? */metal A 4food intake+ & Baverage weight where /metal, 4food intake and Baverage weight represent the heav metal concentrations in plants *@g&g+, dail intake of vegetables and average bod weight, respectivel . !ealth 'isk ,ndex The health risk index can be calculated as the ratio of estimated exposure of test crops and oral reference dose. Estimated exposure is obtained b dividing dail intake of heav metals b their safe limits. 2n index more than 1 is considered as not safe for human health. 4. Permissible Limits of Heavy metals and their effects $.1 !imits for some of t e ea,y metals in some food stuffs areC

$.2 *ealt effects of ea,y metals 2rsenic Eower level exposure can cause nausea and vomiting, decreased production of red and white blood cells, abnormal heart rh thm, damage to blood vessels, and a sensation of Fpins and needlesG in hands and feet. ,ngestion of ver high levels can possibl result in death. Eong-term low level exposure can cause a darkening of the skin and the appearance of small FcornsG or FwartsG on the palms, soles, and torso. /admium ,ngesting ver high levels severel irritates the stomach, leading to vomiting and diarrhoea. Eong-term exposure to lower levels leads to a build up in the kidne s and possible kidne disease, lung damage, and fragile bones. /hromium Breathing high levels can cause irritation to the lining of the nose, nose ulcers, runn nose, and breathing problems, such as asthma, cough, shortness of breath, or wheezing. #kin contact can cause skin ulcers. 2llergic reactions consisting of severe redness and swelling of the skin have been noted. Eong term exposure can cause damage to liver, kidne circulator and nerve tissues, as well as skin irritation. Eead Exposure to high lead levels can severel damage the brain and kidne s and ultimatel cause death ,n pregnant women, high levels of exposure to lead ma cause miscarriage. !igh level exposure in men and women can cause reproductive problems. 0ercur The nervous s stem is ver sensitive to all forms of mercur . Exposure to high levels can permanentl damage the brain, kidne s, and developing foetuses. Effects on brain functioning ma result in irritabilit , sh ness, tremors, changes in vision or hearing, and memor problems. #hort-term exposure to high levels of metallic mercur vapours ma cause lung damage, nausea, vomiting, diarrhoea, increases in blood pressure or heart rate, skin rashes, and e e irritation. #elenium #hort-term oral exposure to high concentrations can cause nausea, vomiting, and diarrhoea. /hronic oral exposure to high concentrations can cause #elenosis. 0a"or signs of selenosis are hair loss, nail brittleness, and neurological abnormalities. Brief exposures to high levels in air can result in respirator tract irritation, bronchitis, difficult breathing, and stomach pains. Eonger-term exposure can cause respirator irritation, bronchial spasms, and coughing.
D

#ilver Exposure to high levels for a long period ma result in a condition called 2r gria, a bluegra discoloration of the skin and other bod tissues. 2rg ria appears to be a cosmetic problem that ma not be otherwise harmful to health. Exposure to high levels of silver in the air has resulted in breathing problems, lung and throat irritation, and stomach pains. #kin contact with silver can cause mild allergic reactions such as rash, swelling, and inflammation in some people.

5. ase !tudies %.1 *ealt risk assessment of ea,y metals ,ia dietary intake of foodstuffs from t e -aste-ater irrigated site at .aranasi EocationC 2round 4inapur sewage treatment plant *4#T(+ situated at a suburban area in the north east of Varanasi cit in eastern Iangetic plains of ,ndia during 0arch 399D to 7ebruar 399H. 2 large area around 4#T( has no access to clean water resources, so farmers use treated and untreated wastewater for irrigation. #oil and water samples were collected at fortnightl interval from 0arch 399D to 7ebruar 399H. 2ll the ma"or vegetables and cereal crops grown in the experimental area, either for home consumption or sale, were collected. 2nal sisC /oncentrations of /d, /u, (b, .n, 1i and /r in the filtrate of digested samples were estimated b using an atomic absorption spectrophotometer. The instrument was fitted with specific lamp of particular metal and calibrated using manuall prepared standard solution of respective heav metals. 'esultsC The range and mean concentrations *@g&g+ of heav metals in soil of wastewater *)),+ and clean water irrigated */),+ sites.

Enrichment factor of heav metals in collected foodstuffs from the experimental site

nf? not found !ealth risk index *!',+ of heav metals via intake of foodstuffs from wastewater irrigated sites

/onclusionsC The health risk index of heav metals suggest that /d, (b and 1i contamination in most of the test plants had potential for human health risk due to consumption of plants grown at waste water irrigated site. 0ilk is found to be least contaminated b heav metals as its health risk index was lower compared to other foodstuffs. The health risk index of cereals was higher than vegetables due to higher proportion of cereals in the diet. /onsumption of foodstuff with elevated levels of heav metals ma lead to high level of accumulation in the bod causing related health disorders. The stud suggests that even
8

though there are low concentrations of heav metals in irrigation water, its long term use caused heav metal contamination leading to health risk of consumers. %.2 *ea,y metals concentrations in ,egetables gro-n near dumpsite in Tan/ania EocationC ,n the cultivation sites in the vicinit of the closed 0toni dumpsite *< km from the cit centre+ 4ar es #alaam, Tanzania, during 7ebruar 3911 to Kul 3911. The dumpsite was receiving waste from the three 0unicipalities of ,lala, Temeke and Linondoni, and an average of 899-1399 tonnes of different waste materials were disposed off at the site dail . The dumpsite was untimel closed in Kanuar 399H due to the manifested serious environmental implications. Based on the surve , it was found that the current soil used for cultivation is the land reclaimed from the ocean gulf through crude dumping of waste materials. The green vegetables Amarant us blitum, &ucurbita ma0ima *pumpkin leaves+, Ipomea batata, .igna unguiculata *cowpea leaves+ and Solanum nigram are the most grown vegetables in the site. 2nal sisC The dr ashing method was used followed b atomic absorption spectrophotometric anal sis. 7or anal tical -ualit assurance, after ever five sample readings, standards were run to make sure that the margin of error is within ;M. The detection limit was 9.91 ppm, slit width 9.H9 nm and elements wavelength were 338.8, 6;H.J, 63<.8 and 386.6 nm for /d, /r, /u and (b, respectivel . 'esultsC !eav metal concentrations in vegetables

/onclusionC The soil in the dumpsite is highl contaminated as indicated in the literature. This stud shows that it is highl risk to human health when consuming vegetables grown in the dumpsite. ,t is necessar to take measures both to stop cultivating vegetables and to conduct communit awareness on the risks associated with dumpsite. The presence of heav metals .n, (b, /u, /r and /d in the edible vegetables A. blitum, &. ma0ima, I. batata1
J

.. unguiculata and S. nigram indicate that the area is not suitable for vegetables production and animal keeping.

%.3 *ea,y metal status in soil and ,egetables in urban areas of Alla abad EocationC The current stud was carried out in the around 2llahabad industrial processing zone *2,(.+, at 1aini located in 2llahabad district, Nttar (radesh, ,ndia from 4ecember 3913 to Kune 3916. The stud area is situated in the south side of the river Ianga J km south of 2llahabad cit . 1aini 2llahabad municipalit has a conventional sewage treatment plant and final treated effluent from the treatment plant is directl taken to the ad"oining agricultural land. The common vegetable grown in the stud area is tomato, spinach, coriander, radish, cabbage etc. which are supplied to the all vegetables market in 2llahabad and the rest entire the common market. 2nal sisC #amples of soils and vegetables were collected randoml in triplicate from effluent-contaminated agricultural land. 2fter digesting, heav metal concentrations of wastewater, soil and vegetable samples were estimated b atomic absorption spectrometer. 'esultsC !eav metal concentrations *mg&E+ in wastewater used for irrigation

/oncentration of heav metals in wastewater irrigated soil *mg&kg dr soil+

19

!eav metal concentration *mg&kg dr weight+ in vegetables grown in waste-water irrigated agricultural landC 0ean and *'ange+

Bioconcentration 7actor&Enrichment factor of the stud area

/onclusionsC 7rom the results of the present stud it is clear that the elevated level of metal accumulation in edible parts of vegetable plants is mainl from their growth habitat like water and soil in and around industrial areas of 1aini 2llahabad. Eong term consumption of these metal-contaminated vegetables can cause different disease like Brain and Lidne damage, cancer in human bod , dermatitis. The data generated must be used as baseline wastewater -ualit framework to serve as a basis for monitoring irrigation water -ualit in rurban areas of 2llahabad to ensure safet . 'esponsible agencies should carr out public health education within the consumption area to sensitive the general public on the potential effects of indiscriminate disposal of waste and the potential health hazards associated with the consumption of vegetables cultivated with wastewater. 0easures must be taken to reduce heav metal pollution and nutrient loading of irrigation water and soils to protect the safet of both farmers and consumers.

11

"eferences
#ingh, 2nita., #harma, 'L., 2grawal, 0., 0arshall, 70.*3919+. !ealth risk assessment of heav metals via dietar intake of foodstuffs from the wastewater irrigated site of a dr tropical area of ,ndia. 7ood and /hemical Toxicolog <8 *3919+ D11=D1J Oadav, 2., Oadav, (L., #hukla, 41.*3916+. ,nvestigation of heav metal status in soil and vegetables grown in urban area of 2llahabad, Nttar (radesh, ,ndia. ,nternational Kournal of #cientific and 'esearch (ublications, Vol6 *J+, 3916 Lihampa, /., 0wegoha, )K#., #hemdoe, '#.*3911+. !eav metals concentrations in vegetables grown in the vicinit of the closed dumpsite. ,nternational Kournal of Environmental #ciences, Vol3 *3+, 3911 4ohert , V7., #ogbanmu, T5., Lanife, N/., )right, 5.*3913+. Ilobal 2dvanced 'esearch Kournal of Environmental #cience and Toxicolog . Vol 1*D+,16H-1<3, 3913*8+ ,brahim, 2. 2rif., !aseeb, 2 Lhan., 2li, 2.2l !omaidan., 2nis 2hamed.*3911+. 4etermination of /u, 0g, !g, (b and .n in the outer tissue )ashings, 5uter Tissues and ,nner Tissues of different vegetables using ,/(-5E#. (olish K. 5f Environ. #tud. Vol 39 *<+ *3911+, 86;-8<1
#tefanut, 01., 4avid,,., #tanoiev, .., 0acarie, /.*399H+. The monitoring of heav metals in fruits. /hem. Bull. P(5E,TE!1,/2P Nniv. *TimiQoara+. Vol ;3*DD+, 1-3, 399H

#harma, 'L., 2grawal, 0., 0arshall, 70.*399J+. !eav metals in vegetables collected from production and market sites of a tropical urban area of ,ndia. 7ood and /hemical Toxicolog <H *399J+ ;86=;J1 /!#', Environmental #cience and Technolog briefs for citizens.399J*6+-1;, !uman health effects of heav metals European Nnion, 399D. /ommission 'egulation *E/+ 1o. 1881&399D of 1J 4ecember 399D #etting 0aximum Eevels for /ertain /ontaminants in foodstuffs. 5ff. K. Eur. Nnion E. 6D<&;

13